Allyl, haloalkyl metal compounds



United States Patent 3,372,176 ALLYL, HALOALKYL METAL COMPQUNDS Frank F. Roselli, San Mateo, Calif., assignor to Diamond Shamrock Corporation, a corporation of Delaware No Drawing. Original application Apr. 15, 1963, Ser. No. 272,882, now Patent No. 3,299,173, dated Jan. 17, 1967. Divided and this application Aug. 29, 1966, Ser. No. 590,129

10 Claims. (Cl. 260-4295) ABSTRACT 6F THE DHSCLOSURE Compounds of the formula (R O),,M(OR wherein M is selected from the group consisting of antimony, titanium, silicon, arsenic, tin, lead and bismuth; R is an allyl radical; R is a 2,3-dihalopropyl radical; a and b are integers from 1 to 4, inclusive; and a+b is an integer from 3 to 5, are prepared by reacting a stoichiometric amount of halogen with an unsaturated ester of the formula (R O) M e.g. triallyl antimonite. The unsaturated ester may be prepared by reacting the corresponding alcohol with a metal halide. The halogenation reaction is preferably carried out in an inert solvent. These compounds are useful as fire-retardant additives in curable polyesters. The olefinic group of the additives participate in the polymerization with the result that the fire-retardant agent is an integral part of the cross-linked resin matrix.

This is a division of application Ser. No. 272,882, filed Apr. 15, 1963, now US. Patent No. 3,299,173.

This invention relates to improved synthetic resins, and more particularly to curable polyesters characterized by improved physical properties and a high degree of fire-resistance; to methods for the preparation of these polyesters and cross-linked resins derived therefrom; and to novel compounds which are useful as fire-retardant additives therein.

One of the principal difficulties to the expansion of the use of synthetic resin in many applications where they otherwise would be highly desirable has been the flammability of the great majority of these resins. To eliminate this disadvantage, a wide variety of fireproofing additives have been developed. Most of these additives contain one or more of a number of elements noted for their fireproofing properties; these elements include bromine, chlorine, phosphorus, and antimony.

In general, prior fireproofing additives are of two varieties. The first variety is incorporated into the resin as a non-reactive filler component. When such an additive is incorporated into a solution of an unsaturated polyester in a liquid monovinyl aromatic compound, it will separate or precipitate during the subsequent curing process, thus altering the light-transmitting properties of the cured resin. This phenomenon is particularly disadvantageous in a transparent resin. Other disadvantages are also encountered when a filler type additive is used. First, the dilution of the resin by the filler may cause a loss in physical strength and hardness. Second, the filler tends to migrate to the surface of the resin and undefgo hydrolysis when it comes in contact with moist air. The result is a loss of fire-resistant properties in the resin as a whole.

Among the filler-type fireproofing agents in the prior art are alkyl and acyl derivatives of antimonous acid. These compounds are effective as fire-retardants and have a minimum effect on the properties of the resin when the latter contains not more than about 5% by weight of the additive. When the additive constitutes as much as 20% of the resin, however, all of the disadvantages described hereinabove are encountered in varying degrees.

3,372,176 Patented Mar. 5, 1968 Thus, the additive acts as a filler and also has some of the characteristics of a plasticizer, with the result that the hardness and strength of the resin are decreased; further, these additives are quite readily extracted from the resin by contacting with water and certain other solvents.

The second variety of fireproofing additive is characterized by its property of reacting with the resin in some Way to become part of its molecular structure. The great advantage of this type of additive is, of course, that it avoids most of the difliculties encountered when a filler additive is used. Since it is part of the molecular rather than an extraneous ingredient, it cannot migrate or be extracted by water or the like; and since it is not a filler it can have no dilution effect on the physical properties of the resin. However, it will be appreciated that the properties of the resin will depend, to a considerable extent, on its structure, and the reacting additive may, therefore have a deleterious effect.

A principal object of this invention, is to provide improved synthetic resins, especially polyesters, and novel compounds for use as fire-retardant agents in polyester resins.

A further object is to provide fire-retardant agents which can be used in higher percentages in the resin than the agents previously developed.

Another object is to provide reactive fire-retardant additives that can be incorporated into the molecular structure of cross-linked polyester without having an adverse effect on its physical and chemical properties.

Still another object is to provide a fire-resistant polyester resin with improved transparency, hardness and chemical stability.

These and other objects are attained by this invention which comprises certain novel fireproofing additives; methods for their preparation; curable, fire-resistant polyester compositions containing these additives; fire-resistant, cross-linked polyester resins, and methods for their preparation.

THE PRESENT INVENTION The novel fire-resistant, curable polyester compositions of this invention comprise: (A) about 3083% by Weight of the reaction product of (1) about 2.02.5 molar parts of at least one aliphatic polyhydroxy compound, (2) about .4-2.0 molar parts of a compound selected from the group consisting of dibasic carboxylic acids containing a polymerizable double bond and anhydrides thereof, and (3) about 0-1.6 molar parts of a compound selected from the group consisting of non-polymerizable dibasic carboxylic acids and anhydrides thereof; (B) about 15- 68% by weight of a solvent for said reaction product, said solvent comprising a monovinyl aromatic compound; and, (C) as a reactive fire-retardant additive, about 2 30% by weight of a compound of the formula wherein M is selected from the group consisting of antimony, titanium, boron, silicon, arsenic, tin, lead, bismuth and phosphorus; R is an aliphatic olefinic radical; R is a radical derived from R by addition across the olefinic bond of halogen of atomic weight 35-80, inclusive; a and b are integers from 1 to 4, inclusive and a+b is an integer from 3 to 5, inclusive.

Illustrative of the novel compounds which may be used as reactive fire-retardant additives according to this invention are the following:

Allyl bis (2,3-dibromopropyl) antimonite CH =CHCH OSb (OCH CHBrCH Br) 2 Diallyl 2,3-dibromopropyl antimonite CH =CHCH O ZSbOCHgCHB rCH Br 3 Allyl tetrakis (2,3 -dibron1opropyl) antimonate CH =CHCH OSb (OCH CHB rCH Br) Diallyl tris(2,3-dibromopropyl) antimonate (cn cncn o 8b (OCH CHBrCH Br) 3 Allyl tris 2,3 -dibromopropyl) titanate CH CHCH OTi(OCH CHBrCH Br) Allyl bis (2,3-dibromopropyl) borate CH =CHCH OB (OCH CHBrCl-I Br) 2 Allyl tris (2,3 -dibromopropyl) silicate CH =CHCH OSi (OCH CHBrCI-I Br) 3 Diallyl bis(2,3-dibromopropyl) silicate (CH =CHCH O Si (OCH CHBrCH Br) 2 The novel compounds of this invention may be prepared by the reaction of the stoichiometric amount of chlorine or bromine with an ester of the formula (R O) M, wherein R a and b are as defined hereinabove. For example, allyl bis(2,3-dibromopropyl) antimonite is prepared by reacting triallyl antimonite with bromine in a mole ratio of 1:2, while diallyl 2,3-dibromopropyl antimonite is prepared from the same reagents in a mole ratio of 1:1. The unsaturated ester starting material is conveniently prepared by reacting the corresponding alcohol with the metal halide, e.g., SbCl SbCl TiCl, or SiCl preferably in the presence of a scavenger such as ammonia or an amine; or by reacting said alcohol with the oxyacid of the metal, e.g., H 30 The halogenation reaction is desirably, but not necessarily, carried out in an inert solvent; halogenated solvents such as carbon tetrachloride, chloroform, methylene chloride and the like are preferred. Reaction temperatures between about -30 C. and +25 C. are satisfactory; the preferred temperature range is from about 15 C. to about C.

The novel compounds of this invention may often be purified by distillation if desired; however, purification is generally not necessary if the compound is to be used as a fire-proofing additive. Many of these compounds are high-boiling and viscous, and therefore very hard to distill.

The polyesters used in this invention are preferably .prepared from at least one aliphatic polyhydroxy compound and a mixture of a dibasic carboxylic acid containing a polymerizable double bond and a non-polymerizable dibasic carboxylic acid. Among the polyhydroxy compounds which may be used are ethylene glycol, propylene glycol, glycerol, and the like. Suitable polymerizable acids include maleic, fumaric, itaconic and citraconic acids and the like; the non-polymerizable acid may be, for example, phthalic, isop-hthalic, terephthalic, succinic or adipic acid or halogenated derivatives thereof.

The role of the polymerizable acid in the resin mix is,

of course, to provide sites for cross-linking. The formed polyester is generally dissolved in a cross-linking agent, usually a monovinyl aromatic compound such as styrene, methylstyrene, vinylpyridine or substituted derivatives thereof. When reaction between the polyester and the cross-linking agent is initiated (for example, by adding a free radical initiator such as benzoyl peroxide), there results a tough, infusible resin.

v When the novel fireproofing agents of this invention are added to the polyester-cross-linker mixture and a catalyst is subsequently added, the allyl groups participate in the polymerization. The result is that the cross-linked resin matrix contains, as an integral part thereof, the fireretardant agent. Thus, adverse effects of a filler additive on the physical properties of the resin are avoided, and there is no migration of the additive to the surface and subsequent hydrolysis to impair transparency.

An alternative method for the preparation of a fireproof polyester is to incorporate the novel additives of this invention into the polyester reaction mixture itself, prior to addition of the cross-linker. Generally, about 0.l0.5 molar part of the additive is used per 2.0-2.5 molar parts of polyhydroxy compound. The terminal hydroxy groups of the growing polyester chain then undergo an exchange reaction with the allyl groups of the additive, and the latter becomes part of the polyester backbone as follows:

l O CHzCEBrOHzBl' If desired, the additive may be incorporated into the polyester and also into the solution prior to curing, thus providing an extra degree of fire-retardancy.

According to the preferred mode of carrying out this invention, a mixture of polymerizable and non-polymerizable dibasic carboxylic acids or anhydrides thereof, as described hereinabove, is esterified with an aliphatic polyhydroxy compound. The two acids are ordinarily used in approximately equimolar amounts, although an excess of either may be used if desired. Enough polyhydroxy compound is usually employed to provide an excess of about 10-25% over the stoichiometric amount. Alternatively, an excess of acid may be used and the carboxy-terminated polyester may be capped with a suitable monohydroxy alcohol, e.g., dibromopropanol.

The polyester formed by the above method is dissolved in the monovinyl aromatic compound, the amount of polyester in the solution usually being about 60-70% by weight. To this solution is added the fireproofing agent, in an amount sutficient to constitute about 230% by weight of the final mixture. When the curing is to be effected, a small amount (e.g., about 0.51.5% by weight) of a free radical polymerization catalyst (or combination of catalysts) is added and the mass is heated to the temperature necessary for cross-linking.

The flame retardant resins of this invention by means of incorporation of suitable promoters and accelerators for instance cobalt naphthenate and dimethyl aniline are curable at room temperature without loss of properties.

The polyesters of this invention are transparent; their strength is comparable to that of untreated resins; and the effect of water or other solvents on their properties is negligible. These properties are found even in resins containing high percentages of additive. In this respect resins made with the antimony compounds are markedly superior to resins containing prior art antimony additives of the filler type.

The following illustrative examples are given in order that those skilled in the art may achieve a fuller understanding of the invention and the preferred means for effecting the same. All parts and percentages are by weight.

Example 1 Preparation of triallyl antim0nite.-In a two-liter, three-necked flask, placed in an ice-water bath at 5 C. and equipped with mechanical stirrer, reflux condenser, thermometer, drying tube and gas inlet, is placed 228 g. (one mole) of anhydrous antimony trichloride crystals dissolved in 1000 ml. of benzene. To this solution, while stirring vigorously, is rapidly added 255 g. (4.4 moles) of allyl alcohol. A gentle stream of anhydrous ammonia gas is introduced under the surface of the solution. A white precipitate of antimony-amine complex starts separating as a fine suspension while the flask temperature is maintained at less than 10 C. As an excess of ammonia is ascertained by the color change of a piece of litmus paper held on top of the reflux condenser, its flow into the flask is discontinued. The temperature is then raised to 79 (3., the reflux temperature of the benzene solution, and this temperature is kept constant for six hours, during which period abundant quantities of ammonia gas are evolved and a crystalline, white precipitate of anhydrous ammonium chloride is formed. The flask is then cooled to room temperature and the precipitate, also containing unreacted antimony trichlorideamine complex, is separated in a nitrogen atmosphere by centrifuging. The filtrate, containing triallyl antimonite is distilled at atmospheric pressure and under nitrogen at 76.8-79 C. to separate the benzene and excess allyl alcohol mixture. The residual of this distillation is a light colored, heavy liquid which hydrolyzes on exposure to the atmosphere. On vacuum distillation of this compound 220 g. (75% of the theoretical amount) of a water-white, heavy liquid is obtained, B.P. 160 C./30 mm. Hg. An elemental analysis of this triallyl antimonite, C H O Sb, gives the following results:

Actual percent By Calculated percent Element Weight By Weight Example 2 Preparation of diallyl 2,3-dibrm0propyl antim0nite. In a 1000 ml., three-necked flask equipped with mechanical stirrer, dropping funnel and drying tube, is placed a solution of 58.4 g. (0.2 mole) of triallyl antimonite in 400 ml. of methylene chloride. The flask is cooled to 10 C. and, while stirring, a solution of 32 g. (0.1 mole) of bromine in 100 ml. of methylene chloride is added at the speed of one drop per second. The bromine absorption by the double bond is instantaneous and exothermic. At the end of the bromination, a colorles solution is obtained. The temperature is allowed to rise to 25 C. and stirring is continued for one hour. The solvent is removed by distillation at 2030 C./100-150 mm. Hg in a nitrogen atmosphere and 90 g. of a very light-colored, liquid residue is obtained which will not. distill. This residue has a Gardner-Holdt viscosity of 17 stokes at 25 C.

Example 3 Preparation of allyl bis(2,3-dibr0m0propyl) antimonite.In a one liter, three-necked flask, equipped as for Example 2, is placed a solution of 58.4 g. (0.2 mole) of triallyl antimonite in 400 ml. of methylene chloride. The flask is cooled to l0 C. and, while stirring, a solution of 64 g. (0.4 mole) of bromine in 100 ml. of methylene chloride is added at one drop per second. The bromine color is rapidly eliminated by reaction with the allyl double bond. Distillation of the solvent at 25-30 C./ 150 mm. Hg in a nitrogen atmosphere leaves 122 g. of a light-colored liquid which will not distill and has a Gardner-Holdt viscosity of 27 stokes at 25 C.

Example 4 Preparation of pentallyl antim0nate.-In a three liter, three-necked flask, equipped as for Example 1, is placed a solution of 150 g. (0.5 mole) of antimony pentachloride in 1500 ml. of n-heptane and 232 g. (4 moles) of allyl alcohol. The flask with its contents is then cooled to 23C. by means of an ice-water bath and a gentle stream of anhydrous ammonia gas is slowly introduced below the surface of the solution while stirring. A finely dispersed, white precipitate of SbCl l0NH starts to form and the solution color turns brown. As an excess of ammonia gas is observed in the solution, its flow into the flask is discontinued and the temperature is slowly raised to reflux. Refluxing is continued for eight hours. A clear brown solution is obtained and the precipitate of ammonium chloride together with the antimony-amine complex is rapidly filtered through coarse filter paper While exposed to the air. No appreciable hydrolysis of the pentallyl antimonate takes place, as compared to the triallyl ester which is readily hydrolyzed. The distillation of heptane and excess allyl alcohol is carried out at 45 50 C./150 mm. Hg in a nitrogen atmosphere. About 120 6 gm. of a brownish product of the theoretical amount), having a viscosity of 1-2 stokes at 25 C., is obtained. The product contains 29% antimony, as compared with the theoretical amount of 30%.

Example 5 Preparation of diallyl tris(2,3-dibr0m0propyl) antimonate.In a one liter, three-necked flask, equipped as for Example 2 and maintained at 5 C., is placed a solution of 20.3 g. (0.05 mole) of pentallyl antimonate in 300 ml. of methylene chloride; 24 g. (0.15 mole) of bromine dissolved in 200 ml. of methylene chloride is added at one drop per second while stirring. All of the bromine is rapidly absorbed as it is added and a light-colored solution is obtained. The solvent is distilled at 30 C./ mm. Hg in a nitrogen atmosphere and 44.0 g. of very thick (Gardner-Holdt viscosity of 35-40 stokes at 25 C.), light-brownish material is obtained which is very stable to hydrolysis.

Example 6 Preparation of allyl tetrakis(2,S-dibromopropyl) antim0naze.-In a one liter, three-necked flask, equipped as for Example 2 and maintained at 5 C., is placed 20.3 g. (0.05 mole) of pentallyl antimonate in 300 ml. of methylene chloride; 32 g. (0.2 mole) of bromine in 200 ml. of methylene chloride is added from a separatory funnel at the speed of one drop per second. The bromine color rapidly disappears as it is absorbed and a tancolored solution is obtained at the end of the bromination. The methylene chloride is distilled off under a nitrogen atmosphere at 30 C./ mm. Hg. The product, a very thick, dark material, is left at the bottom of the flask. The yield is 52 g.

Example 7 Preparation of tetrallyl titanate.-One hundred-ninety grams (one mole) of titanium tetrachloride is dissolved in 1000 ml. of cyclohexane and the solution is placed in a two-liter, three-necked flask equipped with mechanical stirrer, reflux condenser, calcium chloride drying tube and gas inlet. Anhydrous ammonia gas is bubbled slowly below the surface of the solution while stirring and the flask temperature is maintained at 5 C. by means of an ice-water bath. A finely dispersed, yellow precipitate indicates the formation of a titanium tetrachloride-ammonia complex. As soon as the presence of an excess of ammonia is ascertained the gas flow is discontinued and the flask temperature is elevated to 2530 C. A separate four-liter resin kettle, equipped with a mechanical stirrer and reflux condenser and adjacent to the three-necked flask described above, is charged with 400 g. (6.9 moles) of allyl alcohol and brought to boiling temperature by means of a heating mantle. The slurry of titanium tetra chloride-ammonia complex in cyclohexane is slowly transferred by nitrogen pressure through a connecting tube into the resin kettle. Reflux is continued for five hours and then the kettle temperature is all-owed to drop to 25 C. The white precipitate of ammonium chloride and excess titanium-ammonia complex is separated by filtration. The cyclohexane solution of tetrallyl titanate is distilled at atmospheric pressure under nitrogen and the solvent with the excess of allyl alcohol distills at 72 C. Toward the end of the solvent distillation a heavy, clear liquid is obtained. To avoid cross-linking of tetrallyl titanate during the vacuum distillation, 1000 parts per million of hydroquinone inhibitor is added. The hydroquinone forms a yellow complex with the product but distillation at 156 C./1 mm. Hg gives a water-white product. The titanium content is 18.5% as compared to a theoretical value of 17.4%

Example 8 Prep'aartion of allyl tris(2,3-dibrom0propyl) titanate.- To 27.6 g. (0.1 mole) of tetrallyl titanate in 300 ml. of methylene chloride, placed in a one liter, three-necked I? 8 flask equipped as in Example 2, is added at one drop cate in 200 ml. of methylene chloride. A solution of 64 per second, from a separatory funnel, 48 g. (0.3 mole) g. (0.4 mole) of bromine in 100 ml. of methylene chloof bromine dissolved in 200 ml. of methylene chloride. ride is added over a period of two hours at 3-5 C., Bromination of the allyl double bond is fast and spon- While stirring. Bromine absorption is rapid and exotaneous and a light-yellow, clear solution is obtained. 5 therrnic and a water-clear solution is obtained. Distilla- The methylene chloride is distilled at 30-35 C./ 150 mm. tion of the solvent at atmospheric pressure gives a light Hg and 75 g. of a light-colored, clear product is obcolored compound which has a viscosity of less than 1 tained which has a Gardner-Holdt viscosity of 3.5 stokes stoke at 25 C. at 25 C. Examples 14-22 Example 9 10 Part APreparatin of polyester laminates.-A poly- Prepamfio" tiiallyl 51151381351! 0 ester is prepared from 2.2 moles of propylene glycol, 1.0 1110131 amOlmtS of allyl alcohol and boric acid in benzene mole of fumaric acid and 1.0 mole of phthalic anhydride. is heated under reflux; the water formed in the reaction To 9 parts f a 5% solution f this polyester in styrene is Collectfid in a Dean & Stark P- When evolution of r is added parts of a fireproor'ing additive as indicated water ceases, the benzene is removed by vacuum distillain Table I, ft which of cumene hydroperoxide tion and the triallyl borate is distilled, Bl 75-77" C./ 12 and 5% f bwzoyl peroxide are introduced A 1 OZ /s-inch thick fiberglass mat is impregnated with the resin Example 10 solution and cured in an oven at 220 F. for two hours. Preparation of allyl bis(2,3-dibr0m0pr0pyl) b0rate.- T appearance of the laminates after curing is Shown To one mole of triallyl borate, at a temperature between 111 Table I, Column 15 and +10 C., is added tw moles of b i with The following tests are carried out on the laminates stirring. The clear product is used without purification in Prepamd yf foregoing method, and 8150 On a Standthe polyester compositions as described hereinafter. ginlf l y the Same PIOCBdllIG but C i g a 1 we. Example 11 29 Part BHardness.Hardness of cured laminates is Preparation of tetrallyl silicate.-In a 500-ml, threemeasured with a Barcol impressor. This apparatus gives necked flask, fitted with a mechanical stirrer, reflux con- 3 r ading of 85-87 on an aluminum test coupon and 100 denser and dropping funnel, are placed a solution of 46.4 011 glaSS- Readings the Coupons P p according g. (0.8 mole) of allyl alcohol and 63.3 g. (0.8 mole) of 30 to Part A are given in column B of Table I. pyridine in 100 ml. of carbon tetrachloride. The solution rt C-W1I r oak & boil tests.Four l /z-inch is stirred and 34 g. (0.2 mole) of silicon tetrachloride qu e, m h-edged pieces are cut frrn each of the is added at such a rate that the mixture is maintained coupons of Part A with a diamond blade saw. One piece at gentle reflux, After the addition of the silicon tetrais retained as a standard, the second is treated With boilcl' loride, refluxing is continued for one hour, 35 ing Water for fifteen minutes, the third iS boiled for 0110 The white precipitate of pyridine hydrochloride which i100! and the fourth iS immersed in water at 112 F. for is formed during the reaction is filtered and weighed in 0116 absence of m i t d fou d t b 78 g, o 84.5% f The coupons are dried at 60 C. and visual comparison the theoretical amount. The solvent is distilled at 7477 is m s o blooming and corrosive effects. The re- C. Upon vacuum distillation of the product, 43 g. of a u are g v n in ColumnC of Table I. clear liquid is obtained, 13.1 119 c./17 mm. Hg. This Part DS0lv@nr extraction-A Weighed -i c se quantity corresponds to 84.4% of the theoretical amount. tion from each of the laminates of Part A is Submerged ill 100 ml. of refluxing methanol for two hours and then dried at 200 F. for two hours. The dried coupon is again weighed and percentage Weight loss is calculated. Column Example 12 Preparation of allyl tris(2,3-dibr0m0propyl) silicate.

In a 500 ml., three-necked flask, equipped as for Exam- 40 D of Tablelshows the results. ple 2, is placed a solution of 91 g. (0.36 mole) of tet- Part E-Bnrning rate.-A 5 /2inch coupon of each rallyl silicate in 200 ml. of methylene chloride. A solulaminate is contacted with a Globar heating element at tion of 171 g. (1.08 moles) of bromine in 100 ml. of 900 C. for three minutes, according to ASTM method methylene chloride is slowly added at 3-5 C., while D757-49. The burning rate in inches per minute is restirring. The bromine color is rapidly dissipated during ported in Table I, Column E.

the addition and a water-white solution is formed. Distillation of the solvent at atmospheric pressure gives 262 Examples 23-25 g. of a light-colored product which has a viscosity of 1.5

to 2 stokes at C- A high unsaturation polyester is prepared from 2.2

5 moles of propylene glycol, 1.33 moles of fumaric acid and 0.67 mole of phthalic anhydride. To a solution of Preparation of diallyl bi.s(2,3 dibromopropyl) silithis polyester in styrene is added a fireproofing additive cate.In a 500 ml., three-necked flask, equipped as for and the tests described hereinabove are performed. Results Example 2, is placed 51.2 g. (0.2 mole) of tetrallyl siliare given in Table I.

Example 13 TABLE I A B O D E F Example Additive Hardness Soak and Boil Extraction Burning Rate Appearance None (control) 45-40 Good 0.07 0.72 Transparent. Allyl bis(2,3-dibron1opropyl)antimouite- 43 Same as control 0.89 0. 505 Do. Diallyl 2,3-dibr0mopropyl antimonite i5 .do 0.035 0. 537 D0. Allyl bis(2,3-dibromopropyl borate 48 0. 6 0.5 Do. Allyl tris(2,3-dibrom0propyl)Silicate a 52 0. 34 0. 5 D0. Diallyl bis(2,3-dibromopropyl)silicate 50 0. 214 0. 49 Do. Tris(n-octyl)antimonite l5 Opaqu 1.05 0.77 Do. Tris(n-octoxy)antimony dibromide 0 Opaque, deteriorated.-. 11. 9 0. 605 Yellow,

non-transparent. Antimony einnamate 38 Opaque 1. 7 0.69 Transparent. Allyl bis(2,3-dibrornopropyl)borate, 20% 40 0.32 Do. Allyl bis(2,3-dibromopropyl)borate, 30% 35 0. 19 Do. None(eontr0l) 53 0. Do.

*Irior art additives.

.9 Example 26 Part APreparatin of polyester laminate.In a resin kettle fitted with a mechanical stirrer, reflux condenser, thermometer and nitrogen inlet are placed 0.89 mole of propylene glycol and 0.4 mole of tetrachlorophthalic anhydride. The kettle is heated to 180 C. and the mixture is allowed to react, with stirring, until an acid value of 11 mg. KOH per gram of resin is attained. Fumaric acid, 0.6 mole, is then added and the reaction is continued at 195 C. until the acid value is 65. The acid value is reduced to 45 by the addition of 0.06 mole of tn'methylolethane, and then to 22 by the addition of 0.24 mole of dibromopropanol. The resulting polyester has a viscosity of 4.6 stokes at 25 C. in 30% styrene.

Sixty-seven parts of the polyester prepared as described above is dissolved in 33 parts of styrene. To this solution is added 12 parts of allyl bis(2,3-dibromopropyl)antimonite. The resulting curable polyester is used to prepare translucent fiberglass laminates which are tested by the procedures described below, in comparison with laminates prepared from the same polyester containing no antimonite and from a typical fire-retardant polyester of commerce.

Part BUnderwriters laboratories bench test-A 12" x 2" X A fiberglass laminate, prepared according to Part A, is suspended in a vertical position, and the lower end is contacted for thirty seconds with the inner cone of a Bunsen flame at 1300:50" F. The time for which the laminate continues to burn after the flame is removed is measured; this time must be no more than fourteen seconds in order to pass the test. Results are given in Table II.

TABLE II Burning time, Polyester seconds Part A (with additive) less than 3 Part A-no additive 108 Commercial product 12 Part C-Tunnel Test.ThiS test measures flamespread characteristics of the test specimens in comparison with an asbestos-cement board (rated 0) and a red oak board (rated 100) of identical size. The ratings are classified as follows:

Non-combustible 0 to 25 Fire-retardant 25 to 50 Slow-burning 50 to 75 Combustible 75 to 200 Highly combustible over 200 When tested by this procedure, the polyester prepared according to Part A has a rating of 10. By comparison, a typical fire-retardant polyester of commerce has a rating 10 of 40-75, and ordinary polyester panels have ratings of over 400.

It is to be understood that while the invention has been described with particular reference to specific embodiments thereof, it is not to be so limited, since changes and modifications therein may be made which are within the full intended scope of the invention as defined in the appended claims.

What is claimed is:

1. Compounds of the formula (R O) M(OR wherein M is selected from the group consisting of antimony, titanium, silicon, arsenic, tin, lead, and bismuth; R is an allyl radical; R is a radical derived from- R by addition across the olefinic bond of a halogoen of atomic weight 35-80, inclusive; a and b are integers of 1 to 4, inclusive; and a+b is an integer from 3 to 5, inclusive, and equals the valence of M.

2. Compounds of the formula (R O) Sb(OR wherein R is an allyl radical; R is a radical derived from R by addition across the olefinic bond of a halogen of atomic weight 35-80, inclusive; and n is an integer from 1 to 2, inclusive.

. Allyl bis(2,3-dibromopropyl)antimonite.

. Diallyl 2,3-dibromopropyl antimonite.

. Allyl tetrakis(2,3-dibromopropy1)antimonate.

. Diallyl tris(2,3-dibromopropyl)antimonate.

. Allyl tris(2,3-dibromopropyl)titanate.

. Allyl tris(2,3-dibromopropyl)silicate.

9. Diallyl bis(2,3-dibromopropyl) silicate.

10. The method for the preparation of a compound according to claim 1 which comprises reacting b molar parts of a halogen of atomic weight 35-80 with one molar part of a compound of the formula (R O) M, wherein M is selected from the group consisting of antimony, titanium, silicon, arsenic, tin, lead, and bismuth; R is an allyl radical; a and b are integers from 1 to 4 inclusive; and a+b is an integer from 3 to 5, inclusive, and equals the valence of M.

References Cited UNITED STATES PATENTS 3,189,565 6/1965 Woods et a1 260462 X 3,223,755 12/1965 Rimmer 260-986 OTHER REFERENCES Sommer et al., J. Amer. Chem. Soc., vol. 70, pp. 2872 and 2873 (1948).

Berichte, vol. 9, pp. 486 and 487, (1876).

Berichte, vol. 10, pp. 1655b (July-December 1877).

Berichte, vol. 12, pp. 132a (January-June 1879).

TOBIAS E. LEVOW, Primary Examiner.

H. M. S. SNEED, Assistant Examiner. 

